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Patented Oct. 29, 1940 1 UNITED STATES PATENT OFFICE AZVO; DYESTUFFS Maxsch mid, Riehen, Switzerland, assignor to the firm Society of ChemicalIndustry in Basle,

Basel, Switzerland No Drawing. Original application May 14, 1937,}Serial No. 142,719, which is a division of application Serial No.108,902, November 2, 1936.

Divided and this application January 5, 1938, 7 Serial No. 183,535. InSwitzerland November I NH @Q I N112 in which a: is a diphenyl linking ora bridge such or a heterocyclic ring such as and the like, and R1 is theresidue of an organic acid, and condensing in known "manner, aftersaponifying the radical of the organic'acid, if this is present, with asuitable ketocompound to pro:

duce a pyrazolone capable of being coupled, The new compounds, whichcorrespond withthe general formula f 'i I l 7 By in which at has themeaning ascribed to it above,

R1 stands for hydrogen or a radical of an organic acid and Py representsthe pyrazolone radical, can

be converted into new azo dyestuffs either by,

coupling them with diazo-compounds or by saponifying any radical of anorganic acid that may be present, then diazotizing and coupling. ith cou-8C1aims. (01. 260160) pling components or by using both reactionstogether.

The new azo dyestufis are characterized by the presence of the atomgrouping in which Py and :1: have the meaning ascribed to them above andin which at least one azo-group I is attached either to the pyrazoloneradical or to the benzene nucleus which is not directly bound to thepyrazolone nucleus. They are particularly suitable for dyeing textilesconsistingof or'containing native or regenerated cellulose. The fastnessof the dyeing may in many cases be improved by I after-treatment withagents yielding metals, whereby metal complexes are formed on the fiber,Suchmetal complexes maybe produced also in the dyeebath, in substance,or during the formatio n of dyestuffs I l As parentgsubstance iorcompounds of the general formula there may be mentioned benzidine,diphenyline of the formula tolidine,'dianisidine, diphenetidine,thioaniline, 4 4' -diaminodiphenyl ether, 4 4' -diaminostilbene,4:4'-diaminodibenzyls, 4:4- or 3:3-.di-

aminodiphenylinethane, 4:4 diaminodiphenylamines, 4:4- or 4:3'- or 3:4'-or 3:3.-diaminobenzoylaniline, lifl' -diiilllil'lOdiPhBhYl urea, the icondensation product from 2 or 3 mol metaphen yleneediamine orpara-phenylenediamine and 1 mol cyanuric chloride or the condensation.product from 1 mol cyanuric chloride, 1' mol aniline andgz molpara-phenylenediamine or meta-phenylenediamine or similarly constructedcondensationproducts in whichthe cyanuric ring is 're-, placed-bysimilarsix -membered hetero rings containing carbon and nitrogen, suchas those. ofthe pyrimidinathe quinazoline, the phthalazine, and

the like, which corresponds to products in which the linkage a: can beformulated for example as Compounds of the general formula aretherefore, for example, monoformylbenzidine, monoacetylbenzidine,monobenzoylbenzidine, 4- or 3-acetylamino-1-(4 or 3-amino)-benzoylaminobenzene, 4-amino-1-(4'- or 3'- acetylamino)-benzoylaminobenzene 3' sulfonic acid, products obtained bymonobenzoylation or monoacetylation from the reduced condensationproducts from 1 mol urea chloride or isocy'anate' from paraormeta-nitraniline and 1 mol 1:4- 45 diaminobenzene-3-sulfonic acid, suchas NH W HOH

NH.CO.CH3

50 S 0311 O CH:

the ternary condensation products from 1 mol 1:4- or1:3-diaminobenzene-3- or -4-sulfonic acid, 1 mol monoacetyl-paraormeta-phenylenediamine and 1 mol of a primary or secondary amine and 1mol cyanuric chloride such as H N H I NH fi Nilooom N N 60 tom ENG-O cmand the like.

there are derived the products which correspond with the aforesaidgeneral formula Such pyrazolones are, for example, the following:

( i003 C- N\ H III-(1;) o

coon

I so=H I CH fi O E C=N\ n /N\ I I NON-C 0- N112 II CHz-C OOOCH: o 0

and so on, as indicated in the fifth paragraph of this specification.

Among the diazo-compounds which may be coupled with such products theremust first be named the simple diazo-compounds, such as diazobenzene,diazonaphthalene, diazotoluene, di-

azoanisole, diazophenetole, diazotized aminoazobenzene or the like andsulfonic acids of them. Of particular interest are, however, thediazocompounds which have in orthoor peri-position to the diazo-group ahydroxyl group or a carboxyl group. Such diazo-compounds are, forexample, those of ortho-aminophenols, ortho-aminonaphthols and theirsulfonic, acids, the diazo-compounds of 1:8-aminonaphthol sulfonicacids, also of ortho-aminocarboxylic acids, for instance anthranilicacid. With the aid of such compounds dyestufis are obtained which can beconverted into valuable metal compounds on the fiber or in substance bymeans of agents which yield metal, for instance copper salts, chromiumsalts or hydroxides of these metals.

Of these dyestufis those are of especial value which are obtained bytreating with copper on the fiber or in substance the azo-dyestuffswhich are themselves obtained by coupling the intermediate'product ofthe general formula with a dia'zotized ortho-amino-carboxylic acid ofthe benzene series. -Thes'e' new dyestuffs .'are therefore the coppercompounds of dyestuffs of the general formula in which R2 stands "for anaromatic nucleus of the benzene series whichcarries a' COOH-group inortho-position to the -N= N group; when R1 is a radicalof a polybasicacid, for instance dibasic acid, these dyestuffs may be formulatedgenerally as follows: y

further coupling components or by treatment with a 'diazo-c'ompound.When the dyestuffs have been made withflthe aid of ortho-aminophenols,ortho-aminocarboxylic acids or their esters or ethers, or whenthey'contain the salicyclic acid grouping or other lake-forminggroups ofatoms they are capable of conversion into metal compounds. Suitablemetals coming into question besides the copper and chromium alreadymentioned are nickel, cobalt, iron, zinc or the like. The metalcompounds may be obtained either on the fiber or in substance.

The new azo dyestufls obtainable according to the present processcorrespond to the general formula inwhich R stands for a nucleusselected from the group consisting of aromatic nucleiof the benzene andnaphthalene "series, 1/ stands fora member of ,the group consisting ofH, methyl, phenyl, 0001-1 and COO-alkyl, :1: stands for a member of thegroup of linkages consisting of a wherein R stands for an aromaticnucleus of the benzene series which is substituted in ortho-position tothe --N=N-group by a COOH-group, 1/ stands for a member of the groupconsisting of H, methyl, phenyl, COOI-I and COO-alkyl, w

stands for a member of the group of linkages consisting of a diphenyllinkage, --O, -S-, -CI-I=C'I-I-, -CH2--CH2, CH2, -NH--,

and a heterocyclic six-membered ring consisting of at least 3 and notexceeding 4 carbon atoms,

and at least 2 and not exceeding 3 nitrogen atoms,

not more than 2 nitrogen atoms standing adja- 55 cent to each other,which ring further contains at least twice and not more than three timesthe atom grouping :75 be diazotized on the fiber and developed by centto each other, which ring further contains at least twice and not morethan three times the atom grouping -N-o t. hewherein the group does notbelongv to the heterocyclic radi-- c'aLZandZ'stands for a member of'agroup of substituents' linked to the benzene nucleus by N-atoms andconsisting of a member of the group consisting of -N=NR1, R1 standingfor an aromatic nucleus from the group consisting which dyestuffs are'yellow to brown and black.

powders dissolving in water to yellow to orange, to'brown to blackishand to green solutions, and dyeing the fiber similar tints of goodfastness.

The following examples illustrate the invention, the parts being byweight:

Example 1 12 2.6'part's of finely ground monoacetylben zi- 7 dine arestirred in 50 parts of water and some ice with 30 parts of hydrochloricacid of specific gravity 1.15. Into this mixture there is dropped slowlyat -10" C. a solution of 7 parts of sodium nitrite in about 20 parts ofwater and when the addition of this nitrite is complete the whole isstirred for about 1 hour and .then filtered.

The filtered diazo-solution is run at 0-5 .0. while stirring well intoan externally cooled-.mixture of 100 parts of stannous chloride of about10 63 per cent. strength and '50 parts of hydrochloric acid of specificgravity 1.15.

The hydrazine thus formed is sparingly soluble. After stirring for about,12 hours the :mixture is filtered and the solid matter washed withdilute hydrochloric acid and then with water. By stirring this solidmatter, if desired after separation of the tin, with dilute alkali thefree hydrazine of the formula is obtained. From alcohol it crystallizesin the form of bright yellow needles of melting point 227 (3.Alternatively the filtered diazo-so'lution is run whilst stirring into amixture of 632 parts of bisulfite liquor of 40 per cent. strength, '30parts of sodium carbonate and 50 parts ofcaustic soda solution of 36 B.Stirring is continued during the night and the product is salted out andfiltered. The filter cake is stirred into 2000 parts of water and afteraddition of 60 parts of acetic acid the whole is heated to boiling.There are then added gradually about 60 parts of zinc dust and boilingis continued until the mass is decolorized. After filtering hot thehydrazin .sulfonic acid of-the formula H OHS-NEFNH QQNH. c 0. c H; 40

is salted out from the cool filtrate.

The hydrazine sulfonic acid can be .converted into the hydrochloride ofthe hydrazine base by treatment with hydrochloric acid.

In like manner products can be prepared from the parent materialsindicated in the 5th paragraph of this specification.

Example .2

The hydrazine hydrochloride of the formula H CI-NHT-NHQQ-NH. o 0 CH;

obtainable as described in paragraphs 1-3 of Example 1 isboiled'together with500 parts of water and 100 parts of hydrochloricacid of specific gravity of 1.15 for about 2-3 hours, whereby thehydrochloride is dissolved. If desired the solution may be treated withsulfurated hydrogen to remove tin, if necessary, filtered and cooled.The large part of the hydrochloride separates and a further quantity maybe salted out from the mother liquor or the latter may be treated withalkali to recover the free base. 7

This base may be recrystallized from alcohol when it forms whitecrystals of melting point 179 C. which become brown on exposure to airand correspond with the formula The corresponding product frommono-acetylortho, ortho'-tolidine crystallizes from alcohol in whitelaminae of melting point 184 C. It has the formula CH. CH:

Example 3 24.1 parts of the hydrazine of Example 1 are dissolved inabout 200 parts of alcohol mixed with some glacial acetic acid. Therearethen added 14 parts .of .ethylaceto-acetate and the mixture isboiledfor about 1 hour. After cooling there are added to the mixture 20 partsof caustic soda solution of 36 B. and the mixture is stirred for 24hours. By heating the larger part of the alcohol is'expelled while wateris substituted, the whole is filtered and pyrazolone precipitated byadding acid. It corresponds with the formula (EH1 I I v /NONH.CO.CH:CHI-("J The condensation may also start from the hydrazine hydrochlorideand be conducted in aqueous medium. In similar manner products areobtained from the other hydrazines indicated in Example 1. Instead ofethylaceto-acetate any other fl-keto-carboxylic acid ester, for instanceethyl benzoyl acetate, terephthaloyl di-acetic ester, ethyl oxal-acetateor the sodium compounds thereof may be used.

Erample 4 27.2 parts of the hydrazine hydrochloride of Example .2 aresuspended in .hot water. Condensation follows with '14 parts ofethylacetoacetate at about 60 C. with gradual neutralization of the acidliberated in the condensation. When the condensation is complete thewhole is cooled, made alkaline to phenolphthalein by means of causticalkali, stirred for 12 hours, heated until everything has been dissolvedand finally the pyrazolone precipitated by neutralization. Itcorresponds with the formula This new product is a white powder ofmelting point 194 (3., soluble in dilute caustic soda solution anddilute mineral acid.

Example 5 30.7 parts ofl-phenyl-(4-phenyl-4"acetylamino-3-methyl-5-pyrazolone of the formulaCH; t=N I \NOONH. o 0.011; H2 C -C i heated and the dyestufi salted outand isolated as usual. It is an orange-yellow powder and dyes cotton'yellow tints. sponds with the formula H QHz' N ONMQC'H,

By substituting for the diaaotized enlistmeused dyestuffs which can bemetallized-are produced.

sulfoanthranilic acid and 1-phenyl-(4'-phenyl- 4-acetylamino) -3 methyl5 pyrazolone produces yellow tints on viscose artificial silk or naturalsilk which become fast to light whenafter-treated with copper; "Thecopper com-" pound of the dyestuif dyes itself cotton yellow tints.

Further products dyeing yellow to brown-red tints are obtained byreplacement of thesulfo- 1 anthranilic acid byortho-amino-phenolesulfonic' acids of the benzene or naphthalene series,such as sulfo-amino-salicylic acid, 4-chloro-2-aminophenol-G-sulfonicacid, 4-nit'r'o-2-aminophenolfi-sulfonic acid,

son: N=Nl p n con The dyestuif, corre Thus, for example the dyestufffrom'dia zotized" 1-amino 2 hydroxy-naphthalene-4-sulfonic acid,2-amino-l-hydroxynaphthalene-4'z8-disulfonic acid, etc., and conversionof the new azo-dyestuffs into their copper com- Similar dyestuffs Leanbe obtained by replacing the 1 phenyl (4 phenyl--,4"-acetylamino) -3- 1which' is substituted by another organic acid radical. H Such acidradicals may be radicals of mono-carboxylic acids, such as propionicacid, butyric acid, capric acid, benzoic acid, cinnamic acid,sulfobenzoic acid, and the like. The acetyl radical of the4"-acetylamino -group can also be replaced by radicals of dicarboxylicacids, such as carbonic acid, oxalic acid,,fumaric acid or maleic acid,phthalic 'acids and sulfo-phthalic acid, two or also-only one carboxylicacid group being amidated. Finally, the 4.' NI-Iz-group may besubstituted by such acid radicals which are not carboxylic acidradicals. As examples of these there may be cited the radicals of theparatoluene-sulfonic acids or the cyanuric acid. The

introductionof such radicals into the dyestuffs of the general formulafollowing formulas:

or thecopper complexes of the dyestuffs of the COOH o 5 2 2 3 3 a. O S

w H H 0 m; w H v0 8 0 w 0' m G O O H m a A N N l m nuv i O CIN l N CIIHa E a N H A v m N H p N H N N N 0 0 N 0H0 H a H O C U H m N 0H0 O O J H"w C mW nV H m N a N H a a N 0 m 0 CI 0| 0' H. O S

H H a 0 O O s S S 0 F0 0 5 9 2 3 3 'SOaH I 40 NH2 poundsamino-carboxylic acids -oxy- NH S 03H This latter dyestufi dyes cottongreen tints.

In all these dyestuffs which correspond to the ener l formula 50 g aThese dyestufis are above all valuable as metal compounds, and thenparticularly as copper 50 compounds. If in these dyestufis thediazotizing component R2 (cf. 10th paragraph of this specification) isan ortho-aminocarboxylic acid of the 55 benzene series, the tintsobtained therewith on cotton, artificial silk or natural silk areusually an stands for a dlphenyl linkage. Dyestuffs havyellow Thedyeings of the copper com ing similar properties are those in which a:is anwhich derive from orthm other linkage cited in the introduction.Comof the naphthalene series or from ortho 6O pare also the lastparagraph of Examp e 1 and diam-compounds of the benzene or naphthalenethe last paragraph of Example 3. Examples of such dyestuffs are:

COOH

series are orange'to' brown-red; Thus, fo m. Me the dyestufi of theformula I yields on cotton yellow tints. Thecomplex ;cop-' per,chromium, nickel and cobalt compounds of this dyestuff yield alsoyellowtints on cotton. The iron compound yields brownish yellow tints.

The copper compound of the dyestuff of the formula and a. heterocycli'c'six me'mbered ring consisting of at least 3 and not exceeding 4 carbonatoms, and at least 2 and not exceeding 3 nitrogen atoms, not more than2 nitrogen atoms stand- 311; G=N I OH I 303K I .L /N I tit A ll JOSH Y.h r son-1 OH is an orange-brownpowder dyeing the fiber orange-browntints, and the dyestuii of the foris a brown-black powder dyeing thefiber claret tints. 7. g

A further strong dyeing dyestufi-can be produced as follows: 59.1 partsof the dyestufi from diazotized dehydrothiotoluidine sulfonic acid andl-phenyl-(4-phenyl-4"amino) 3 methyl- 5-pyrazolone are treated in theusual manner with phosgene. When the reaction is complete the dyestufiformed is isolated.

It is a brown powder and dyes cellulose fibers:

' and 2: stands for the group consisting of fast orange tints.

In my copending application Serial No. 183,534, filed January 5, 1938,(being also a division of my application-SerialNo. 142,719 filed on May14, 1937) there-have beendescribed sulfonated asymmetrical azo dyestufiscontaining at least two azo-groupsof the general formula member of thegroupconsistingof H, methyl phenyl, COOH and COO-alkyl, a3-,stands for amemberof the group of linkages consisting of a ing adjacent to eachother, which ring mam contains at least twice and not more than threetimes theatom grouping wherein the group does not belong to theheterocyclic radical,

N=NR1, R1 standin for an aromatic nucleus from the group consisting ofaromatic nuclei of the benzene and naphthalene series, and complex metalcompounds of these dyestuffs. No claim' is made herein to dyestufiscontaining no metal in complex union.

What I claim is:

1. The sulfonated azo dyestuffs containing at least one azo-group andcorresponding to the general formula I I in which R stands for a nucleusselected from the group consisting of aromatic nuclei of the benzene andnaphthalene series, '1 stands for a member of the group consisting of H,methyl, phenyl, 00011 and COO-alkyl, :1: stands for a member of thegroup of linkages consisting of a diphenyl linkage, O, -S, --CH=CH-,CH2CH2, --CI-Iz, NH-,

' t --C-N,N'C,NJ 'II I I II I 0 H H 0 H and a heterocyclic six-memberedring consisting of at least 3 and not exceeding 4 carbon atoms, and atleast 2 and not exceeding 3 nitrogen atoms, not more than 2 nitrogenatoms standing adjacent to each other, which ring further contains atleast twice and not more than three times the atom grouping wherein thegroup does not belong to the heterocyclic radical and which is linked atleast twice to the phenyl groups through III 11 groups, R1 stands forthe radical of an azo dyestufi, and in which general formula further thegroups and l t i do not stand in ortho-position to one another, whichdyestuffs are yellow to brown and black powders dissolving in water toyellow to orange, to brown, to blackish and to green solutions, anddyeing the fiber similar tints of good fastness.

2. The sulfonated azo dyestuffs containing at least two azo-groups andcorresponding to the general formula in which R1 and R2 stand foraromatic nuclei selected from the group consisting of nuclei of thebenzene and naphthalene series which are substituted in ortho-positionto the N=N- group by a substituent selected from the group consisting ofOH- and COOH-groups, 0: stands for a member of the group of linkagesconsisting of a diphenyl linkage, O-, S, CH=CH,

and a heterocyclic six-membered ring consisting of at least 3 and notexceeding 4 carbon atoms, and at least 2 and not exceeding 3 nitrogenatoms, not more than 2 nitrogen atoms standing adjacent to each other,which ring further contains at least twice and not more than three timesthe atom grouping H \N wherein the t group does not belong to theheterocyclic radical and which is linked at least twice to the phenylgroups through stand in another position than in ortho-position to oneanother, which dyestufis are yellow to brown powders dissolving in waterto yellow, to orange and to brown solutions and dyeing the fiber similartints which become faster when after-treated with copper salts.

3. The sulfonated azo dyestuffs containing at least two azo-groups andcorresponding to the general formula in which y stands for a member ofthe group wherein R stands for an aromatic nucleus selected from thegroup consisting of nuclei of the benzene and naphthalene series whichis substituted in ortho-position to the N=Ngroup by roup consistin :1}stands for a g of H, methyl,

a. substituent selected from the g of OH and COOH groups, and

g group, and. 1 stands for a. member of the group consisting of H,methyl, phenyl, COOH and. member of the group consistin COO-alkyl, whichdyestuffs are yellow to phenyl, COOH and COOalkyl, which dyestufisbrown-yellow powders dissolving in water to 5 are yellow to orange andbrownish powders disyellow solutions, and producing on cotton yellow 5solving in water to similar solutions, and productints. ing on cottonsimilar tints.

6. The dyestufi of the formula (3113 O l-N SOzH 5. The sulfonated azodyestuffs of the general n m N VIJWIIIICIH N C 0 1 J o NlH N "w CH0 u cc H a N m M N .I B 5 0 1 2 wherein R stands for an aromatic nucleus ofthe 7. The dyestufi of the formula benzene series which is substitutedin ortho- 35 position to the N=Ngroup by a. COOI-I- The dyestufi themmula'

